Carbon materials and their allotropes have been involved significantly in our daily lives. Zero-dimensional (0D) fullerenes, one-dimensional (1D) carbon materials, and two-dimensional (2D) graphene materials have distinctive properties and thus received immense attention from the early 2000s. To meet the growing demand for these materials in applications like energy storage, electrochemical catalysis, and environmental remediation, the special category, i.e., three-dimensional (3D) structures assembled from graphene sheets, has been developed. Graphene oxide is a chemically altered graphene, the desired building block for 3D graphene matter (i.e., 3D graphene macrostructures). A simple synthesis route and pore morphologies make 3D reduced-graphene oxide (rGO) a major candidate for the 3D graphene group. To obtain target-specific 3D rGO, its synthesis mechanism plays an important role. Hence, in this article, we will discuss the general mechanism for 3D rGO synthesis, vital procedures for fabricating advanced 3D rGO, and important aspects controlling the growth of 3D rGO.